Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Reexamination Certificate
2000-08-31
2001-05-22
Barts, Samuel (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
Reexamination Certificate
active
06235937
ABSTRACT:
FIELD OF THE INVENTION
The invention relates to a process for the preparation of nitrodiphenylamines, in particular 4-nitrodiphenylamine (4-NDPA), by reaction of nitrohalogenobenzenes with aromatic amines in the presence of a palladium catalyst and a base.
BACKGROUND OF THE INVENTION
The preparation of nitrodiphenylamines by reaction of corresponding aromatic amines with p-nitrochlorobenzene in the presence of an acid acceptor or a neutralizing agent, optionally in the presence of a catalyst, is known and is described, for example, in DE-A 3,246,151.
The disadvantages of the processes described above are often the inadequate selectivities which, in addition to losses in yield, as a rule, necessitate more or less expensive purification steps before the nitrodiphenylamines can be reacted further, for example by hydrogenation to 4-aminodiphenylamines.
A more recent method for the preparation of arylamines by reaction of amines with aromatic compounds, for example, also halogenated nitrobenzenes, in the presence of a palladium catalyst and a base is described in U.S. Pat. No. 5,576,460. It is furthermore known from EP-A 846,676, for example, to react nitrohalogenobenzenes with aromatic amines in the presence of a palladium catalyst, a base and a halide as a co-catalyst.
WO 99/01418 describes the reaction in water with palladium catalysts and water-soluble phosphines. As a rule, the low yields of 20-50% are a disadvantage in this process.
SUMMARY OF THE INVENTION
Therefore, it was desirable to provide a process for the preparation of 4-aminodiphenylamines, which starts from aromatic amines and leads to the desired nitrodiphenylamines in good yields and high purities by reaction of corresponding p-nitrohalogenobenzenes.
The present invention therefore provides a process for the preparation of nitrodiphenylamines by reaction of nitrohalogenobenzenes with aromatic amines in the presence of a base and a palladium catalyst, wherein a palladium-phosphine complex or other palladium complexes are employed as the palladium catalyst; and alkali metal and/or alkaline earth metal carbonates, alcoholates and/or hydroxides are used as bases, the bases being ground and/or dried before their use.
DETAILED DESCRIPTION OF THE INVENTION
Nitrohalogenobenzenes which are preferably employed are those in which the nitro group is in the para-position relative to the halogen radical. Possible halogen radicals are: fluorine, chlorine, bromine and iodine, preferably chlorine and bromine. It is of course possible for the nitrohalogenobenzenes to be further substituted by other radicals, such as, for example, C
1
-C
4
-alkyl radicals. The nitro group can of course also be in a position relative to the halogen radicals other than the para-position, such as in the 2- and 3-position.
Nitrohalogenobenzenes, which may be mentioned are, for example: 4-nitro-2-methylchlorobenzene, 4-nitro-3-methylchlorobenzene, 4-nitrochlorobenzene, 3-nitrochlorobenzene and 2-nitrochlorobenzene. 4-Nitrochlorobenzene is particularly preferred.
Aromatic amines which can be employed in the process according to the present invention are the aromatic amines which are known for such a reaction, for example aniline, o-toluidine, m-toluidine, p-toluidine, 4-ethylaniline, 4-butylaniline, 4-isopropylaniline, 3,5-dimethylaniline and 2,4-dimethylaniline. Aniline is preferred. The aromatic amines can of course also be employed in the form of mixtures, in particular isomeric mixtures.
In the process according to the present invention, 1 to 10 mol, preferably 1.5 to 6 mol, more preferably 2 to 4 mol of the aromatic amine are in general employed per mol of nitrohalogenobenzene.
As mentioned above, catalysts which are particularly suitable for the process according to the present invention are palladium-phosphine complex compounds, where the palladium has the valency 0 or II and possible phosphine ligands are, for example, compounds such as triphenylphosphine, tri-o-toluylphosphine, tricyclohexylphosphine, tri-t-butylphosphine, bisdiphenylphosphine-ethane, bisdiphenyl-phosphinepropane, bisdiphenylphosphinobutane, bisdicyclohexylphosphinoethane, bisdiphenylphosphinoferrocene, 5,5′-dichloro-6,6′-dimethoxy-biphenyl-2,2′-diyl-bisdiphenylphosphine, bis-4,4′-dibenzofuran-3,3′-yl-bisdiphenylphosphine, 1,1′-bisdiphenylphosphino-diphenyl ether and bisdiphenylphosphinobinaphthyl, wherein the phenyl radicals thereof can be substituted by sulfonic acid radicals or can optionally be replaced by one or more C
1
-C
12
-alkyl groups or C
3
-C
10
-cycloalkyl groups. Polymer-bonded phosphines can furthermore also serve as ligands. Triphenylphosphine is preferably used as the ligand.
However, ligands other than the phosphine ligands mentioned can also be employed for the process according to the present invention, such as, for example, nitrogen- or oxygen-containing ligands or also ligands containing two or more different heteroatoms.
Palladium compounds which may be mentioned are, for example, the following compounds: Pd
2
dba
3
, Pd(acac)
2
, Pd(Oac)
2
, PdCl
2
, (CH
3
CN)
2
Pd(NO
2
)Cl and also other palladium halides, such as bromides and iodides, acetates, carbonates, ketonates, nitrates, acetonates or palladacyclic compounds. Heterogeneous or immobilized palladium catalysts can, furthermore, also be employed in the process according to the invention. It is possible here to employ a complex which has already been prepared beforehand or to form a complex in situ from a suitable Pd compound and a ligand.
In the palladium-phosphine complexes to be employed according to the present invention, the ratio of the corresponding ligand to palladium is about 40:1 to 1:1, preferably 10:1 to 2:1, and most preferably 8:1 to 4:1.
According to the present invention, the palladium-phosphine complexes or the other complexes are in general employed in amounts of 0.0001 mol % to 10 mol %, preferably 0.001 mol % to 5 mol %, based on the nitrohalogenobenzenes employed.
Bases which are employed in the process according to the present invention are alkali metal and/or alkaline earth metal carbonates, alcoholates and/or hydroxides, potassium and/or sodium carbonate, caesium carbonate, sodium methanolate and barium hydroxide being mentioned in particular. Potassium and/or sodium carbonate are preferably employed. The bases can be employed in less than the stoichiometric amount or in an excess of up to ten times the equivalent amount with respect to the nitrohalogenobenzene. The bases are most preferably employed in amounts of 0.3 to 2 equivalents, based on the nitrohalogenobenzene.
The process according to the present invention can be carried out at temperatures in the range from 20 to 250° C., but preferably at temperatures of 120 to 180° C. The reaction temperatures here depend, in particular, on the nature of the starting substances, the catalyst and the bases employed.
The process according to the present invention can be carried out both in the presence and in the absence of a suitable solvent. Possible solvents are, for example, inert organic hydrocarbons, such as xylene and toluene. Furthermore, the aromatic amines employed can themselves function as solvents.
In the process described, the water of reaction formed can optionally be removed analogously to DE-A 2,633,811 and DE-A 3,246,151, for example by distillation with the aid of a suitable entraining agent, or this step can also be omitted.
The amount of solvents employed can easily be determined by appropriate preliminary experiments.
It is essential for the process according to the present invention that the bases employed are pretreated by grinding and/or drying.
The grinding in the process according to the present invention can be carried put, for example, in commercially available kitchen or ball mills. The grinding measure here has the effect of a drastic increase in the specific surface area, which leads to a significant increase in the conversion. In many cases, an increase in the specific surface area by a factor of 10 to 20 is to be observed by grinding. In the process described, an
Giera Henry
Lange Walter
Pohl Torsten
Schild Christoph
Sicheneder Adolf
Barts Samuel
Bayer Aktiengesellschaft
Cheung Noland J.
Gil Joseph C.
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